Synergistic compositions comprising an oxathiazine and a benzothiophene-2-carboxamide-S,S-dioxide

ABSTRACT

This invention relates to synergistic compositions of oxathiazines and benzothiophene-2-carboxamide-S,S-dioxides for use as fungicidal preservatives in the protection of materials, such as protection of wood, wood products, biodegradable materials and coatings.

This application is a 371 of 00/006,495 filed Oct. 7, 1998.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the national stage of application no.PCT/EP98/06495, filed Oct. 7, 1998 which application claims priorityfrom EP 97203227.0, filed Oct. 15, 1997.

This invention relates to synergistic compositions of oxathiazines andbenzothiophene-2-carboxamide-S,S-dioxides for use as fungicidalpreservatives in tie protection of materials, such as protection ofwood, wood products, biodegradable materials and coatings.

It now has been found that compositions comprising particular ratios ofan oxathiazine of formula (I) and abenzotihiophene-2-carboxamide-S,Sdioxide of formula (II) exhibitsynergistic fungicidal activity.

The present invention is concerned with compositions comprising anoxathiazine of formula (I), or a salt thereof, and abenzothiophene-2-carboxamide-S,S-dioxide of formula (II), or a saltthereof, in quantities producing a mutual synergistic effect, and acarrier.

The oxathiazines of formula (I) have the following structure

wherein n is 0, 1 or 2; R¹ is hydrogen, C₁₋₄alkyl or benzyl; and R²represents (a) phenyl; phenyl substituted with 1 to 3 substituentsindependently selected from hydroxyl, halo, C₁₋₁₂alkyl, C₅₋₆cycloaLkyl,trihalomethyl, phenyl, C₁₋₅alkoxy, C₁₋₅alkylthio, tetrahydropyranyloxy,phenoxy, C₁₋₅alkycarbonyl, phenylcarbonyl, C₁₋₄alkylsuifinyl,C₁₋₄alkylsulfonyl, carboxy or its alkali metal salt,C₁₋₅alkyloxy-carbonyl, C₁₋₅alkylaminocarbonyl, phenylaminocarbonyl,tolylainocarbonyl, morpholinocarbonyl, amnino, nitro, cyano, dioxolanylor C₁₋₄alkyloxyiminomethyl; naphthyl; pyridinyl; thienyl, preferablywhen n is not 2; furanyl; or thienyl or furanyl substituted with one tothree substituents independently selected from C₁₋₄alkyl, C₁₋₄alkyloxy,C₁₋₄alkylthio, halo, cyano, formyl, acetyl, benzoyl, nitro,C₁₋₄alkyloxy-carbonyl, phenyl, phenylaminocarbonyl andC₁₋₄alkyloxyiminomethyl; or R² represents a radical of formula

wherein X is oxygen or suilfr; Y is nitrogen or CH or C(C₁₋₄allyloxy);and R³ is hydrogen or C₁₋₄akyl.

Said compounds of formula (I) are described in WO-95/06043, published onMar. 2, 1995, as a bactericidal and fungicidal compounds useful inwood-protection. The use of said compounds for the protection ofnon-living materials, in particular the anti-fouling use, is describedin WO-95/05739, published on Mar. 2, 1995. WO95/05739 also describes theantibacterial, anti-yeast, antifungal, algicidal, anti-crustacean andmolluscicidal properties of said compounds of formula (I) andcompositions comprising them.

All compounds of formula (I) can be prepared following the proceduresdescribed in U.S. Pat. No. 4,569,690.

The benzothiophene-2-carboxamide-S,S-dioxides of formula (II) can berepresented by the formula

wherein R⁸ represents straight-chain or branched alkyl having 1 to 20carbon atoms, or represents in each case straight-chain or branchedhalogenoalkyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl oralkoxycarbonylalkyl, each of which has 1 to 8 carbon atoms in theindividual alkyl moieties, or represents straight-chain or branchedalkenyl having 2 to 12 carbon atoms, or represents straight-chain orbranched alkynyl having 2 to 12 carbon atoms, or representscycloalkylalkyl or cycloalkyl, each of which has 3 to 7 carbon atoms inthe cycloalkyl moiety and, in the case of cycloalkylalkyl, 1 to 6 carbonatoms in the straight-chain or branched alkyl moiety, and each of whichis optionally monosubstituted to hexasubstituted in the cycloalky moietyby identical or different substituents, suitable cycloalkyl substituentsin each case being: halogen, in each case straight-chain or branchedalkyl having 1 to 4 carbon atoms or in each case straight-chain orbranched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identicalor different halogen atoms; furthermore represents arylalkyl,arylalkenyl, arylalyynyl or aryl, each of which has 6 or 10 carbon atomsin the aryl moiety and, in the cases of arylalkyl, arylalkenyl andarylalkynyl, up to 12 carbon atoms in the respective straight-chain orbranched alkyl or alkenyl or alkynyl moiety, each of which is optionallymonosubstituted to pentasubstituted in the aryl moiety by identical ordifferent substituents, suitable aryl substituents in each case being:halogen, cyano, nitro, formylamido, in each case straight-chain orbranched alkyl, alkoxy or alkylthio, each of which has 1 to 4 carbonatoms, in each case straight-chain or branched halogenoalkyl,halogenoalkoxy, halogenoalkylthio, each of which has 1 to 4 carbon atomsand 1 to 9 identical or different halogen atoms, in each casestraight-chain or branched alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,N-alkylaminocarbonyl, N,N-dialkyl-aminocarbonyl, alkylcarbonylamino,N-alkyl-alkylcarbonylamino, N-alkylformyl-carbonylamino oralkoximinoalkyl, each of which has 1 to 4 carbon atoms in the individualalkyl moieties, and phenyl which is optionally monosubstituted orpolysubstituted by identical or different substituents from the groupconsisting of halogen and/or straight-chain or branched aLkyl having 1to 4 carbon atoms; R⁹ represents hydrogen or straight-chain or branchedalkyl which has 1 to 6 carbon atoms and which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents, suitable substituents being: hydroxyl, halogen, cyano, andin each case straight-chain or branched alkoxy, alkoxycarbonyl ordialkylamino; each of which has 1 to 6 carbon atoms in the individualakyl moieties; or R⁸ and R⁹ together with the nitrogen atom to whichthey are bonded represent a saturated 5- to 7-membered heterocycle whichis optionally monosubstituted or polysubstituted by identical ordifferent substituents and which can optionally contain 1 or 2 furtherhetero atoms selected from the group consisting of nitrogen, oxygen andsulphur, suitable substituents in each case being: halogen, in each casestraight-chain or branched alkyl, alkoxy or alkoxycarbonyl having ineach case 1 to 4 carbon atoms or straight-chain or branchedhalogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical ordifferent halogen atoms; and

R⁴, R⁵, R⁶ and R⁷ independently of one another in each case representhydrogen, halogen, cyano, nitro or in each case straight-chain orbranched alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy orhalogenoalkylthio each of which has 1 to 6 carbon atoms and, in the caseof halogenoaLky, halogenoalkoxy or halogenoalkylthio, 1 to 13 identicalor different halogen atoms.

Said compounds of formula (II), their preparation and use in plantprotection, the protection of materials and in the field of human andveterinary medicine, are described in EP-0,512,349, published on Nov.11, 1992.

All compounds of formula (II) can be prepared following the proceduresdescribed in EP-0,512,349.

In the foregoing definitions halo is generic to fluoro, chloro, bromoand iodo; C₁₋₄alkyl defines straight and branch chained saturatedhydrocarbon radicals having from 1 to 4 carbon atoms comprising methyl,ethyl, n-propyl, 1-methylethyl, n-butyl, 1,1-dimethyl-ethyl,1-methylpropyl, 2-methylpropyl; C₁₋₅alkyl includes C₁₋₄alkyl radicals asdefined above and saturated hydrocarbon radicals having five carbonatoms, e.g. n-pentyl and the branched pentyl isomers; C₁₋₆alkyl includesC₁₋₅alkyl radicals as defined above and six carbon containinghomologues, e.g. n-hexyl and the branched hexyl isomers; C₁₋₁₂alkylincludes C₁₋₆alkyl and saturated hydrocarbon radicals having from 7 to12 carbon atoms, e.g. heptyl, octyl, nonyl, decyl, undecyl and theirisomers. The term alkali metal cation in particular is a sodiurm orpotassium cation. Trihalomethyl defines a methyl group being fullysubstituted with halo atoms, in particular trifluoromethyl andtrichloromethyl. C₁₋₄alkyloxyiminomethyl defines a radical of formula—CH═N—O—C₁₋₄alkyl. C₅₋₆cycloalkyl comprises cyclopentyl and cyclohexyl.

Particular compounds of formula (I) for use in the method are thosewherein n is 0, 1 or 2; R¹ is hydrogen, C₁₋₄alkyl or benzyl; and R²represents phenyl; naphthyl; pyridinyl; thienyl provided that n is not2; furanyl optionally substituted with 1 to 3 substituents independentlyselected from C₁₋₄alkyl and C₁₋₄alkyloxycarbonyl; or phenyl substitutedwith 1 or 2 substituents independently selected from hydroxyl, halo,C₁₋₁₂alkyl, C₅₋₆cylo-alkyl, trihalomethyl, phenyl, C₁₋₅alkoxy,C₁₋₅alkylthio, tetrahydropyranyloxy, phenoxy, C₁₋₄alkylcarbonyl,phenylcarbonyl, C₁₋₄alkylsulfnyl, C₁₋₄alkylsulfonyl, carboxy or itsalkali metal salt, C₁₋₄aakoxycarbonyl, C₁₋₄alkylaminocarbonyl,phenylaminocarbonyl, tolylaminocarbonyl, morpholinocarbonyl, amino,nitro, cyano, or dioxolanyl.

Of interest are those compounds of formula (I) wherein n is 1 and R²represents phenyl, thienyl or phenyl substituted with one or twosubstituents selected from halo and trihalomethyl; or those wherein n is2 and R² represents phenyl or phenyl substituted with one or twosubstituents selected from halo and trihalomethyl.

Of further interest are the compounds of formula (I) wherein R¹ ishydrogen, n is 1 or 2, and R² represents phenyl, C₁₋₆alkylphenyl,halophenyl, dihalophenyl, biphenyl, C₁₋₅alkyloxyphenyl,trihalomethylphenyl, nitrophenyl, phenyl substituted withC₁₋₄alkyloxycarbonyl, C₁₋₆alkylnitrophenyl, unsubstitluted fiinyl orthienyl, or furanyl or thienyl substituted with ethoxycarbonyl, cyano,chlorine or bromine.

Of particular interest are the compounds of formula (1) wherein R¹ ishydrogen, n is 1 or 2, and R² represents 3-fluorophenyl, 4-chlorophenyl,3,4-dichlorophenyl, 3,5-dichlorophenyl, 3-trifluoromethylphenyl,4-trifluoromethylphenyl, 4-methylphenyl, 3-ethanonephenyl, 3-nitrophenyL3-methyl-4-nitrophenyl or 2-thienyl.

Also of further interest are those compounds of formula (I) wherein R¹is hydrogen, R² is a radical of formula (b) wherein X is sulfur, Y isnitrogen or CH, and R³ is hydrogen.

The most preferred compound of formula (I) is3-(benzo[b]thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine, 4-oxide,generically known as “bethoxazin”, and referred to as “compound (1)”throughout the description, having formula:

Particular compounds of formula (II) are those compounds of formula (II)wherein wherein R⁸ represents methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, n- or i-pentyl, 20 n- or i-hexyl, n- or i-heptyl, n- ori-octyl, n- or i-nonyl, n- or i-decyl, n- or i-dodecyl, n- ori-octadecyl, alkyl, n- or i-butenyl, n- or i-pentenyl, n- or i-hexenyl,propargyl, n- or i-butinyl, n- or i-pentinyl, n- or i-hexinyl,chloromethyl, bromomethyl, chloroethyl, bromoethyl, chloropropylbromopropyl, cyanomethyl, cyanoethyl, cyanopropyl, hydroxymethyl,hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl,ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxycarbonylmethyl,methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl,ethoxycarbonylethyl, ethoxycarbonylpropyl, propoxycarbonylmethyl,propoxycarbonylethyl, propoxycarbonylpropyl; furthermore representscyclopropyl, cyclopropyhnethyl, cyclopropylethyl, cyclopropylpropyl,cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl,cyclohexyl, cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, eachof which is optionally monosubstituted to tetrasubstituted in thecycloalkyl moiety by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, n- ori-propyl, chloromethyl, dichloromethyl or trifluoromethyl; furthermorerepresents phenylalkyl, phenylalkenyl, phenyl alkynyl, phenyl ornaphthyl, each of which has, in the case of phenylalkyl, phenylalkenyland phenylalkynyl, up to 6 carbon atoms in the straight-chain orbranched alkyl or alkenyl or alkynyl moiety and each of which isoptionally monosubstituted to trisubstituted in the aryl moiety byidentical or different substituents, suitable aryl substituents in eachcase being: fluorine, chlorine, bromine, hydroxyl, cyano, nitro, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- ori-propoxy, n-, i-, s- or t-butoxy, methylthio, ethytltio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylcarbonyl,ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl,N-methylaminocarbonyl, N,Ndmethylaminocarbonyl, N-ethylamino-carbonyl,NN-diethylaminocarbonyl, N-formylamino, N-acetylamino,N-methyl-N-formylamino, N-methyl-N-acetylamino, N-ethyl-N-formylamino,N-ethyl-N-acetylanuo, methoximinomethyl, methoximinoethyl,ethoximinomethyl, ethoximinoethyl, or phenyl which is optionallymonosubstituted to trisubstituted by identical or different substituentsfrom the group consisting of fluorine, chlorine, bromine, methyl and/orethyl;

R⁹ represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- ort-butyl, n- or i-pentyl, n- or i-hexyl, hydroxymethyl, hydroxyethyl,hydroxypropyl, chloromethyl, bromomethyl, chloroethyl, bromoethyl,chloropropyl, bromopropyl, cyanomethyl, cyanoethyl, cyanopropyl,hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl,methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl,methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl,ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl,propoxycarbonylmethyl, propoxycarbonylethyl, propoxycarbonylpropyl,dimethylaminomethyl, diethylanomethyl, dipropylaminomethyl,dimethylaminoethyl, diethylaminoethyl, dipropylaminoethyl,dimethylaminopropyl, diethylaminopropyl ordipropylaminopropyl; or

R⁸ and R⁹ together with the nitrogen atom to which they are bondedrepresent a heterocycle of the formula

 each of which is optionally monosubstituted, disubstituted ortrisubstituted by methyl and/or ethyl and/or methoxycarbonyl and/orethoxycarbonyl;

R⁴, R⁵, R⁶ and R⁷ independently of one another in each case representhydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy n- or i-propoxy, n-,i-, s- or t-butoxy, methylthio, ethylthio, trifluoromethyl,trifluoromethoxy or trifluoromethylthio. referred compounds of formula(II) are those compounds of formula (II) wherein R⁴, ⁵, R⁶ and R⁷ areeach hydrogen; R⁸ is N-butyl, N-pentyl, N-n-hexyl, orN-cyclohexyl-methyl and R⁹ is hydrogen; or wherein R⁸ and R⁹ are takentogether with the nitrogen atom to which they are bonded forming aN-cyclohexyl.

The most preferred compound of formula (II) isN-cyclohexyl-benzothiophene-2-carboxamide-S,S-dioxide, referred to as“compound (2)” throughout the description, having the followingstructure:

The active ingredients (I) and (II) may be present in base or in saltform, the latter being obtained by reaction of the base form with anappropriate acid. Appropriate acids comprise, for example, inorganicacids, such as the hydrohalic acids, i.e. hydrofluoric, hydrochloric,hydrobromic and hydroiodic, sulfuric acid, nitric acid, phosphoric acidand the like; or organic acids, such as, for example, acetic, propanoic,hydroxyacetic, 2-hydroxypropanoic, 2-oxopropanoic, ethanedioic,propanedioic, butanedioic, (Z)-2-butenedioic, (E)-2-butenedioic,2-hydroxybutanedioic, 2,3-dihydroxybutanedioic,2-hydroxy-1,2,3-propanetricarboxylic, methanesulfonic, ethanesulfonic,benzenesulfonic, 4-methylbenzenesulfonic, cyclohexanesulfamic,2-hydroxybenzoic, 4-amino-2-hydroxybenzoic and the like acids.

The term salt form also comprises metal complexes which the basiccomponents (I) or (II) may form. One of the components may occur as acomplex and the other not; or both components may occur as a complex.Metal complexes as mentioned above consist of a complex formed betweenone or more molecules of the active ingredient and one or more organicor inorganic metal salt or salts. Examples of said organic or inorganicsalts comprise the halogenides, nitrates, sulfates, phosphates,acetates, trifluoroacetates, trichloroacetates, propionates, tartrates,sulfonates, e.g. methylsulfonates, 4-methylphenylsulfonates,salicylates, benzoates and the like of the metals of the second maingroup of the periodical system, e.g. the magnesium or calcium salts, ofthe third or fourth main group, e.g. aluminum, tin, lead as well as thefirst to the eighth transition groups of the periodical system such as,for example, chromium, manganese, iron, cobalt, nickel, copper, zinc andthe like. Preferred are the metals pertaining to the transition elementsof the fourth period. The metals may be present in each of theirpossible valences. The metal ions may be present in any of theirpossible valences, the most preferred metal copper being mostadvantageously used in its divalent form Cu(II). Suitable coppercompounds are copper sulfate, acetate, hydroxide, oxide, borate,fluoride and in particular copper hydroxide carbonate Cu(OH)₂CuCO₃. Thecomplexes can be mono- or polynuclear, they may contain one or moreparts of the organic molecule as ligands.

The term salt as used hereinabove also comprises the solvates which theactive ingredients of formula (I) and (II) are able to form. Examples ofsuch solvates are e.g., the hydrates, alcoholates and the like.

The metal salt complexes of the active ingredients of formula (I) or(II) can conveniently be prepared by dissolving the metal salt in asuitable solvent e.g. ethanol, and adding thereto the activeingredients. The thus obtained complexes may be isolated followingart-known techniques, e.g. by filtration or evaporation, and may befurther purified , e.g. by recrystallization. The term salt as usedhereinabove also comprises the solvates which the compounds of formula(I) or (II) are able to form, e.g. hydrates, alcoholates and the like.

The synergistic mixtures or compositions according to the presentinvention are most useful to combat wood-destroying and wood-discoloringfungi or prevent the growth thereof in wood or wood products. As woodwhich can be preserved with the synergistic compositions according tothe present invention is considered, for example, wood products such astimber, lumber, railway sleepers, telephone poles, fences, woodcoverings, wicker-work, windows and doors, plywood, particle board,waferboards, chipboard, joinery, bridges or wood products which aregenerally used in housebuilding, construction and carpentry. Synergisticcompositions according to the present invention can also advantageouslybe applied in the cellulose and paper industry, in particular to protectpulpwood for paper manufacture from final attack; and also inbiodegradable materials such as, for example, textiles of naturalfibers, e.g. cotton, flax, hemp, wool, silk and the like; textiles ofsynthetic fibers, e.g. polyamide, polyacrylonitrile or polyester fibers,or of mixtures of such fibers; coatings, e.g. oil paints, dispersionpaints, lacquers, lacquer films, whitewash, finishing stains and thelike; glues and other such materials which are biodegradable by fungi.

The synergistic mixtures of the present invention are active against abroad range of fungi. As examples of such fungi there may be namedAscomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula,Aureobasidium, Scierophoma); Basidiomycetes (e.g. Hemileia, Rhizoctonia,Puccinia, Coniophora, Serpula, Poria, Uromyces, Gloeophyllum, Lentinus,Coniolus, Irpex); Fungi imperfecti (e.g. Botrytis, Helminthosporium,Rhynchosponium, Fusanium, Septoria, Cercospora, Alternaria, Pyricularia,Penicillium, Geotrichum).

Wood which is preserved from staining, discoloring and decay is meant tobe protected from for example, moulding, rotting, loss of its usefulmechanical properties such as breaking strength, resistance to shock andshearing strength, or decrease of its optical or other useful propertiesdue to the occurrence of odor, staining and spot formation. Thesephenomena are caused by a number of micro-organisms of which thefollowing are typical examples:

Wood-discoloring fungi:

1: Ascomycetes:

Ceratocystis e.g. Ceratocystis minor.

Aureobasidium e.g. Aureobasidium pullulans

Scierophoma e.g. Scierophoma pithyophila

Clidosporium e.g. Cladosporium herbarum

2: Deuteromycetes:

Fungi imperfecti

Aspergillus e.g. Aspergillus niger

Dactylium e.g. Dactylium fusarioides

Penicillium e.g. P. brevicaule, P. variabile, P. funiculosum or P.glaucum

Scopularia e.g. Scopularia phycomyces

Trichoderma e.g. Trichoderma viride or Trichoderma lignorum.

Alternaria e.g. Alternaria tenius, Alternaria alternata

3: Zygomycetes:

Mucor e.g. Mucor spinorus.

Wood-destroying fungi

1: Soft-rot Fungi:

Chaetomium e.g. Ch. globosum or Ch alba-arenulum

Humicola e.g. Humicola grisea

Petriella e.g. Petriella setifera

Trichurus e.g. Trichurus spiralis.

2: White and brown rot Fungi:

Coniophora e.g. Coniophoraputeana

Coriolus e.g. Coriolus versicolor

Donkioporia e.g. Donkioporia expansa

Glenospora e.g. Glenospora graphii

Gloeophyllum e.g. Gl. abietinum, Gl adoratum, Gl. protactum, Gl.sepiarium or Gl. trabeum

Lentinus e.g. L. cyathiformes, L. edodes, L. lepideus, L. grinus or Lsquarrolosus

Paxillus e.g. Paxillus panuoides

Pleurotus e.g. Pleurotis ostreatus

Poria e.g. P. monticola, P. placenta, P. vailiantii or P. vaporaria

Serpula (Merulius) e.g. Serpula himantoides or Serpula lacrymans

Stereum e.g. Stereum hirsutum

Trychophyton e.g. Trychophyton mentagrophytes

Tyromyces e.g. Tyromyces palustris.

In order to protect wood from decay it is treated with synergisticcompositions according to the present invention. Such treatment isapplied by several different procedures such as, for example, bytreating the wood in closed pressure or vacuum systems, in thermal ordip systems and the like, or by a wide variety of surface treatments,e.g. by spraying, atomizing, dusting, scattering, pouring, brushing,dipping, soaking or impregnating the wood with a composition comprisinga compound of formula (I), in particular3-benzo[b]thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine 4-oxide, or a saltthereof, and a compound of formula (II), in particularN-cyclohexylbenzothiophene-2-carboxamide-S,S-dioxide (II), or a saltthereof, in quantities producing a mutual synergistic effect, and acarrier.

The amount of each of the active ingredients of formula (I) and (II) inthe compositions according to the present invention is such that amutual synergistic fungicidal effect is obtained upon application. Inparticular, it is contemplated that in the compositions to be useddirectly, the concentration of a compound of formula (I), in particular3-(benzo[b]thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine, 4-oxide (i.e.compound 1), taken as base equivalent, may range from 10 to 5000 ppm, inparticular from 50 to 2000 ppm or from 50 to 1000 ppm, more inparticular from 100 to 800 ppm; and the concentration of the compound offormula (II), in particularN-cyclohexyl-benzothiophene-2-carboxamide-S,S-dioxide (i.e. compound 2),taken as base equivalent is contemplated to range from 10 to 5000 ppm,in particular from 50 to 2000 ppm or from 100 to 1000 ppm, more inparticular from 200 to 800 ppm. In many instances said compositions tobe used directly can be obtained from concentrates upon dilution withaqueous or organic media, such concentrates also being intended to becovered by the term composition as used in the definitions of thepresent invention. The content of the active ingredients in theabove-indicated compositions is from 0.01 to 95%, preferably from 0.1 to50% more preferably from 0.1 to 20% and in particular from 0.2 to 15% byweight. The compositions according to the invention are preferably usedin the form of solutions or emulsions.

The ratio between the active ingredients of formula (I) and (II) will besuch that a synergistic fingicidal effect is obtained with both activeingredients. Particularly, the weight ratio between (I) and (II) mayrange from 50:1 to 1:50, more particularly from 20:1 to 1:20 andpreferably will range from about 5:1 to 1:5. When the compound offormula (I) is 3-(benzo[b]thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine,4-oxide (i.e. compound 1), and the compound of formula (II) isN-cyclohexyl-benzothiophene-2-carboxamide-S,S-dioxdde (i.e. compound 2),the weight ratio between (I) and (II) preferably ranges from 1:64 to2:1, more particularly from 1:16 to 1:1 and preferably will be from 1:4to 1:2.

The active ingredients of formula (I) and (II) are used in unmodifiedform or together with adjuvants conventionally employed in the art offormulation. The formulations, i.e. the compositions, preparations ormixtures containing the active ingredients and, where appropriate, asolid or liquid adjuvant, are prepared following art-known procedures,e.g. by homogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers and, where appropriate,surface-active compounds (surfactants), to emulsifiable concentrates,directly sprayable or dilutable solutions, dilute emulsions, wettablepowders, soluble powders, dusts, granulates, and also encapsulations ine.g. polymer substances. Both the nature of the compositions and themethods of application such as spraying, atomizing, dusting, scatteringor pouring, brushing, dipping, soaking or impregnating, should be chosenin accordance with the intended objectives and the prevailingcircumstances. It is evident that in general different compositions withdifferent characteristics will be required for use in plant protectionon the one hand, and for use in material protection on the other.Carriers and adjuvants equally useful in both types of compositions aredescribed first.

Appropriate carriers and adjuvants for use in the compositions of thepresent invention may be solid or liquid and correspond to suitablesubstances known in the art for preparing formulations for treatingplants or the loci thereof, or for treating plant products, inparticular for treating wood, such as, for example, natural orregenerated mineral substances, solvents, dispersants, surfactants,wetting agents, adhesives, thickeners, binders, fertilizers, anti-freezeagents, repellents, colour additives, corrosion inhibitors,water-repelling agents, siccatives, UV-stabihizrs and other activeingredients.

The solid carriers used e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated absorbentcarriers are of the porous type, for example pumice, broken brick,sepiolite or bentonite; and suitable nonsorbent carriers are materialssuch as calcite or sand. In addition, a great number of pregranulatedmaterials of inorganic or organic nature can be used, e.g. especiallydolomite or pulverised plant residues.

Suitable solvents are aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. dimethylbenzene mixtures orsubstituted naphthalenes, phthalates such as dibutyl phthalate ordioctyl phthalate, aliphatic or alicyclic hydrocarbons such ascyclohexane or paraffms, alcohols and glycols and their ethers andesters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ormonoethyl ether, ketones such as cyclohexanone, strongly polar solventssuch as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide,as well as vegetable oils or epoxidised vegetable oils such asepoxidised coconut oil or soybean oil; or water, or a mixture of saidsolvents.

Suitable surface-active compounds to be used in the compositions of thepresent invention are non-ionic, cationic and/or anionic surfactantshaving good emulsifying, dispersing and wetting properties. The term“surfactants” will also be understood as comprising mixtures ofsurfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds. Suitable soaps are thealkali metal salts, earth alkaline metal salts or unsubstituted orsubstituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. thesodium or potassium salts of oleic or stearic acid, or of natural fattyacid mixtures which can be obtained e.g. from coconut oil or tallow oil.In addition, there may also be mentioned fatty acid methyltaurin salts.More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylaryl-sulfonates. The fatty sulfonates or sulfatesare usually in the form of alkali metal salts, earth alkaline metalsalts or unsubstituted or substituted ammonium salts and contain analkyl radical having from 8 to 22 carbon atoms said alkyl alsocomprising radicals derived from acyl radicals, e.g. the sodium orcalcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture offatty alcohol sulfates obtained from natural fatty acids. Thesecompounds also comprise the salts of suluric acid esters and sulfonicacids of fatty alcohol/ethylene oxide adducts. The sulfonatedbenzimidazole derivatives preferably contain 2 sulfonic acid groups andone fatty acid radical containing 8 to 22 carbon atoms. Examples ofalkylarylsulfonates are the sodium, calcium or triethanolamine salts ofdodecylbenzene-sulfonic acid, dibutylnaphthalene-sulfonic acid, or of anaphthalenesulfonic acid/formaldehyde condensation product. Alsosuitable are corresponding phosphates, e.g. salts of the phosphoric acidester of an adduct of p-nonylphenol with 4 to 14 moles of ethyleneoxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 10 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol containing 1 to 10 carbon atoms inthe alkyl chain, which adducts contain 20 to 250 ethylene glycol ethergroups and 10 to 100 propylene glycol ether groups. These compoundsusually contain 1 to 5 ethylene glycol units per propylene glycol unit.Representative examples of non-ionic surfactants are nonylphenolpolyethoxy-ethanols, castor oil polyglycol ethers,polypropylenelpolyethylene oxide adducts,tributylphenoxy-polyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Fatty acid esters of polyethylenesorbitan, such as polyoxyethylene sorbitan trioleate, are also suitablenon-ionic surfactants. They are of particular utility in compositionsfor material, in particular wood, protection.

Cationic surfactants are preferably quaternary ammonium salts wherein atleast one N-substituent is a C₈-C₂₂alkyl radical and the furthersubstituents are unsubstituted or halogenated lower alkyl, benzyl orhydroxy lower alkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylanimoniumchloride or benzyldi(2-chloroethyl)ethylammonium bromide. They areparticularly useful in compositions for agrochemical purposes.

The surfactants customarily employed in the art of formulation aredescribed e.g. in the following publications : “McCutcheon's Detergentsand Emulsifiers Annual”, MC Publishing Corp., Ridgewood, N.J., 1981; H.Stache, “Tensid-Taschenbuch”, 2nd Edition, C. Hanser Verlag, Munich &Vienna, 1981, M. and J. Ash, “Encyclopedia of Surfactants”, Vol. I-III,Chemical Publishing Co., New York, 1980-81.

The following paragraphs in particular relate to compositions for use inplant protection. In general such compositions are designed so as to beinnocuous to culture plants, to be easily and safely applicable, to havegood bioavailability to the host plants and to remain (persist) onlytemporarily in the environment.

Particularly advantageous additives useful to improve the applicationand reduce the dose of the active ingredients, are the natural (animalor plant) or synthetic phospholipids of the cephalin or lecithin typesuch as, for example, phosphatidylethanolamine, phosphatidyl serine,phosphatidylglycerine, lysolecithin, or cardiolipin. Such phospholipidsmay be obtained from animal or plant cells, in particular from brain-,heart- or liver tissue, egg yolks or soy beans. Appropriate suchphospholipids are for instance, phosphatidylcholine mixtures. Syntheticphospholipids are for instance, dioctanylphosphatidylcholine anddipalmitoylphosphatidylcholine.

In case of liquid formulations, and particularly of aqueous or alcoholicformulations, it is recommendable to add an appropriate surfactant,either from the anionic, cationic, nonionic or amphoteric type. Inparticular said surfactants will be of the cationic type and more inparticular said surfactant is a quatemary ammonium salt or a mixture ofquaternary ammonium salts. Such quaternary ammonium surfactantscomprise, e.g., ammonium salts having four hydrocarbon radicals whichmay optionally be substituted with halo, phenyl, substituted phenyl orhydroxy; said hydrocarbon radicals in particular being alkyl or alkenylradicals; they may also be derived from fatty acids or alcohols, e.g.cetyl, lauryl, palmityl, myristyl, oleyl and the like or from thehydrosylates form coconut oil, tallow oil, soy bean oiL or thehydrogenated forms thereof, and the like.

Examples of such quaternary ammonium salts are of the trimethyl alkylammonium halide type, e.g. trimethyl decyl ammonium chloride, trimethyldodecylammonium chloride, trimethyl tallow ammonium chloride, trimethyloleyl ammonium chloride; or of the dimethyl alkyl benzyl ammonium type,e.g. dimethyl decyl benzyl ammonium chloride, dimethyldodecyl benzylammonium chloride, dimethyl hexadecylbenzyl ammonium chloride (commonlydesignated as “cetalkonium chloride”), dimethyl octadecyl benzylammonium chloride, dimethyl coco benzyl ammonium chloride, dimethyltallow benzyl ammonium chloride; and particularly the dimethylC₈₋₁₈alkyl benzyl ammonium chloride mixture which is commonly known as“benzalkonium chloride”; dimethyl dialkyl ammonium halides, e.g.dimethyl dioctyl ammonium chloride, dimethyl didecyl ammonium chloride,dimethyl didodecyl ammonium chloride, dimethyl dicoco ammonium chloride,dimethyl ditallow ammonium chloride, dimethyl octyl decyl ammoniumchloride, dimethyl dodecyl octyl ammonium chloride, dimethyldihydrogenated tallow ammonium chloride.

As used in the foregoing enumeration of quaternary ammonium salts, theterms “coco”, “tallow” and “hydrogenated tallow” designate thosehydrocarbon radicals derived from the hydrosylates of coconut oil,tallow oil or hydrogenated tallow oil. The weight ratio between saidquaternary ammonium surfactants and the active ingredients of formula(I) and (II) is situated between 1:1 and 10:1. Excellent results areobtained when said ratio is about 5:1.

The following paragraphs in particular relate to compositions for use inwood protection. In general such compositions are designed so as topenetrate well in to wood, to persist there for a long time, and to beindustrially applicable.

A biocidally active quaternary ammonium compound or tertiary amine saltcan advantageously be used in the formulation of emulsions of the activeingredients of formula (I) and (II) in aqueous solutions of metal salts.Micro-emulsions may thus be formed which have particular utility in woodpreservation. Additional advantages related to these adjuvants comprisetheir solubilizing effect on the active ingredients of formula (I) and(II), their contributory biocidal effect and their ability to promotepenetration of the formulation into wood.

Binders are meant to comprise binding drying oils (e.g. linseed oil) andresins that are water-dilutable or dilutable, dispersible oremulsifiable in organic solvents, e.g. acryl, vinyl, polyester,polyurethane, alkyd, phenolic, hydrocarbon and silicon resins. Mixturesof an alkyd resin with a drying oil are advantageously used as a bindingmaterial. Part of the binding material may further be substituted withone or more fixing agents or one or more plasticizers. These adjuvantsdelay or prevent evaporation of the active ingredients as wellprecipitation or crystallisation thereof. About 0.01% to about 30% ofthe binding material may thus be replaced. Suitable plasticizers arephthalic acid esters, e.g. the dibutyl, dioctyl and benzylbutylphthalate esters; phosphoric acid esters, e.g. tributylphosphate; fattyacid esters, e.g. di(2-ethylhexyl)adipate, butylstearate, amylstearate,butyloleate; glycerolethers; glycolethers; glycerolesters; andp-toluenesulfonic acid esters. Suitable fixing agents are polyvinylalkylethers, e.g. polyvinylmethyl ethers, or ketones, e.g. benzophenone orethylenebenzophenone.

In view of their solubility in organic solvents the active ingredientsare well suited for application in non-aqueous media, which is ofinterest in wood-preservation. The wood or wood products to be protectedcan easily be impregnated with such solutions. As organic solvents theremay be used aliphatic and aromatic hydrocarbons, their chlorinatedderivatives, acid amides, mineral oils, alcohols, ethers, glycolethers,such as, for example, methylene chloride, propylene glycol,methoxyethanol, ethoxyethanol, N,N-dimethylformamide and the like ormixtures of such solvents, to which there may be added dispersants oremulsifiers such as sulfated ricinus oil, fatty alcohol sulfates andother additives.

Particularly attractive formulations comprise water-dilutablewood-preservative liquids containing an appropriate amount of a suitablesolvent, a suitable solubilizer and both the active ingredients.Preferably there is used 10-80% of a solvent, 20-80% of a solubilizerand from 0.01 to 10% of the active ingredients (I) and (II).

Preferred solubilizers to be used in the said water-dilutablewood-preservative liquids are selected from:

i) addition products of 1 to 60 moles of ethylene oxide with 1 mole of aphenol which is further substituted with at least one C₁₋₅alkyl group;and

ii) addition products of 1 to 60 moles of ethylene oxide with 1 mole ofricinus oil.

The most preferred solubilizers are selected from:

i) addition products of 1 to 60 moles of ethylene oxide with 1 mole ofnonylphenol or octylphenol; and

ii) addition products of 1 to 60 moles of ethylene oxide with 1 mole ofricinus oil.

Said suitable solvent should fulfill the requirements of sufficientlysolubilizing the active ingredients and, when combined with thesolubilizer, of being homogeneously miscible with a predominantlyaqueous medium. Preferred solvents are 2-butoxyethanol, butyl2-hydroxyacetic acid ester and propyleneglycol monomethylether.

Preferred water-dilutable compositions for use in wood protectioncomprise active ingredients (I) and (II), a copper compound, suitablesolvents and/or solubility enhancers and optionally other adjuvants.Suitable solvents are e.g. alcohols (ethanol, iso-propanol), glycols(ethylene and propylene glycol), glycolethers (ethylene glycolmonomethyl and monoethyl ether), dimethylformamide, n-methylpyrrolidone,which yield homogenous concentrates. As solubilizers there may beemployed carboxylic acids, or the amine, alkali metal or copper saltforms corresponding thereto, so that the amount of the organic solventused in the homogenous concentrates can be kept to a minimum. Examplesof such acids are propionic, hexanoic, heptanoic, 2-ethylhexanoic,iso-octanoic, sebacic, cyclohexanoic, benzoic, 3-hydroxybenzoic and4-hydroxybenzoic acid. To improve further the industrial applicabilityof such water-dilutable, homogenous compositions comprising a carboxylicacid as solubilizer, advantageous use may be made of polyethyleneimines(PEI, Polymin) derived from ethyleneimine (aziridine) and having theformula (C₂H₅N)_(n). The degree of polymerization ‘n’ should be largerthan 10 and preferably ranges from about 50 to about 1000, and inparticular is about 150. The use of alkanolamines, in particularmonoethanolamine, but also di- and triethanolamine, as complexing agentsfor the copper compound employed may be of particular benefit. Typicallythere may be used about 4 molar equivalents of alkanolamine per mole ofcopper. Further useful additives are, for example, boron derivatives,e.g. boric acid, its salts and esters, and fluorides, e.g. potassiumfluoride.

Water-dilutable homogenous concentrates in particular comprise byweight:

2.5 to 45%, in particular 10 to 20% copper compound,

5 to 50%, in particular 20 to 40% alkanolamine,

0.25 to 15%, in particular 1 to 10% of compounds of formula (I) and(II),

0.5 to 30%, in particular 5 to 15% surfactant(s),

15 0 to 40% other fungicidal compoundis),

0 to 40% organic solvent(s),

0 to 40% carboxylic acid(s), and

0 to 40% polymin.

Said water-dilutable wood-preserving liquids have the advantage thatalmost instantaneously homogeneous or quasi homogeneous solutions areformed by mixing these liquids with predominantly aqueous media Thesesolutions have an extremely high physical stability, not only at ambienttemperature, ie. at temperatures comprised between 15° C. and 35° C.,but also at decreased temperatures. Thus, the physical stability of saidsolutions does not deteriorate after several freeze-thaw cycles. Saidhomogeneous solutions further unite the advantages of moistening thewood-surface well and penetrating the wood to a high degree, resultingin a high uptake of the solution and its active ingredients by the wood,and, consequently, obtaining the desired preservation of the treatedwood. Additionally, due to a more uniform uptake of the aqueous solutionthe wood-preserving liquids and the resulting aqueous solutions areparticularly useful in treatment techniques which require thepossibility of a continuous process, such as, for example, impregnationor dip techniques. In addition, the solutions formed with thewood-preserving liquids unite in themselves the hereinabove mentionedadvantages with those which are characteristic of predominantly aqueousmedia, such as, for example, a relatively high flashpoint and reducedtoxicity, resulting in advantageous influence on the environment and thehealth and safety of the applicator, lack of irritation and the likebenefits.

Apart from both the aforementioned active ingredients of formula (I) and(II), the compositions according to the present invention may furthercontain other active ingredients, e.g. other microbiocides, inparticular insecticides, and also bactericides, acaricides, nematicides,herbicides, plant growth regulators, fertilizers or further fingicides.As antimicrobial agents, which may be used in combination with theactive substances there may be considered products of the followingclasses : phenol derivatives such as 3,5-dichlorophenol,2,5-dichlorophenol, 3,5-dibromophenol, 2,5-dibromophenol, 2,5-(resp.3,5)-dichlorobromophenol, 3,4,5-trichlorophenol, tribromophenol,trtrachlorophenol, 3-methyl-4-chlorophenol; chlorinatedhydroxydiphenylethers such as, for example,2-hydroxy-3,2′4′-trichlorodiphenylether; phenylphenol (o-, m-, p-),4-chloro-2-phenylphenol, 4chloro-2-benzylphenol, dichlorophene,hexachlorophene; aldehydes such as formaldehyde, glutaraldehyde,salicylaldehyde; alcohols such as phenoxyethanol; antimicrobially activecarboxylic acids and their derivatives; organometallic compounds such astributyltin compounds; iodine compounds such as iodophores, iodoniumcompounds; diiodomethyl-p-tolyl-sulfone, 3-iodo-2-propynyl-alkohol,4-chlorophenyl-3-iodopropargyl-formal,3-bromo-2,3-diiodo-2-propenylethylcarb-Rat, 2,3,3-triiodoalkylalkohol,3-bromo-2,3-diiodo-2-propenylalkohol,3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-hexylcarbamate,3-iodo-2-propynyl-cyclohexylcarbamate,3-iodo-2-propynyl-phenyl-carbamate; mono-, di- and polyamines such asdodecylamine or 1,10-di(n-heptyl)-1,10-diaminodecane; sulfonium- andphosphonium compounds; mercapto compounds as well as their alkali, earthalkaline and heavy metal salts such as 2-mercaptopyridine-N-oxide andits sodium, iron, manganese and zinc salt, 3-mercaptopyridazin-2-oxide,2-mercaptoquinoxaline-1-oxide, 2-mercaptoquinoaline-i-N-oxide, as wellas the symmetrical disulfides of said mercapto compounds; ureas such astribromo- or trichlorocarbanilide, dichlorotrifluoromethyl-diphenylurea;tribromosalicylanilide; 2-bromo-2-nitro-1,3-dihydroxypropane (bronopol);dichlorobenzoxazolone; chlorohexidine; sulfenamides e.g. dichlofluanid,tolylfluanid, folpet, fluorfolpet; benzimidazoles e.g. carbendazim,benomyl, fuberidazole, thiabendazole; thiocyanates e.g.thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate; quaternaryammonium compounds e.g. benzyldimethyltetradecyl ammonium chloride,benzyldimethyldodecyl ammonium chloride, didecyldimethyl ammoniumchloride; morpholine derivates e.g. tridemorph, fenpropimorph,falimorph; azoles e.g. triadimefon, triadimenol, bitertanol, prochloraz;2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)3-(1H-1,2,4-triazol-1-yl)-propan-2-ol;isothiazolinones e.g. N-methylisothiazolin-3-one,5-chloro-N-methyl-isothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one;benzisothiazolinone, cyclopenteneisothiazolinone;tetrachloro-4-methylsulfonyl-pyridine; metal salts e.g. tin, copper,zink naphthenate, ctoate, 2-ethylhexanoate, oleate, phosphate, benzoate;oxides e.g. tributyltin oxide, Cu₂O, CuO, ZnO; dialkyldithiocarbamatee.g. Na- and Zn-salts of dialkyldithio-carbamates,tetramethylthiuramdisulfide; nitriles e.g.2,4,5,6-tetrachloroisophthalodinitrile; benzothiazole e.g.2-mercaptobenzothiazole; quinolines e.g. 8-hydroxyquinoline and itsCu-salts; boron compounds e.g. boric acid, boric acid esters, borax;formaldehyde and formaldehyde releasing compounds e.g. benzylalkoholmono(poly)hemiformal oxazolidine, hexahydro-S-triazine,N-methylol-chloracetamide, parafotmaldehyde;tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-cyclohexyl-diazenium-dioxy)-tributyltinbis-N-(cyclohexyldiazeniumdioxy)-copper.

The compositions of the present invention comprising the aforementionedactive ingredients of formula (I) and (II) may further comprise afungicidally active triazole such as, for example, azaconazole(1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole),bromuconazole(1-[4-bromo-2-(2,4-dichloro-phenyl)tetrahydrofurfuryl]-1H-1,2,4-triazole),cyproconazole(α-(4-chlorophenyl)-α-(1-cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol),difenoconazole(1-[2-[4-(4-chlorophenoxy)-2-chlorophenyl]-4-methyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole),epoxiconazole(1-[3-(2-chlorophenyl)-2-(4fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole),fenbuconazole(4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4triazol-1-ylmethyl)-butyronitrile),hexaconazole(α-butyl-α-(2,4-dichlorophenyl)-1H-1,2,4-triazole-1-ethanol),metconazole(5-[(4-chlorophenyl)methyl]-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol),penconazole (1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole),propiconazole(1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole),tebuconazole(α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-ethanol),or triticonazole((E)-5-(4-chlorophenyl)methylene)-2,2-dimethyl-1-(1H-1,2,4triazol-1-ylmethylI)cyclopentanol).

As insecticidal agents which may be used in the combination according tothe present invention the following classes of products may beconsidered: insecticides having a natural origin, e.g., nicotine,rotenone, pyrethrum and the like; chlorinated hydrocarbons, e.g.,lindane, chlordane, endosulfan and the like; organic phosphor compounds,e.g. azinphos-ethyl, azinphos-methyl, 1-(4-chlorphenyl)-4(O-ethyl,S-propyl)phosphoryl-oxypyrazole, chlorpyrifos, coumaphos, demeton,demeton-S-methyl, diazinon, dichlorvos, dimethoate, ethoprophos,etrimfos, fenitrothion, fenthion, heptenophos, parathion,parathionmethyl, phosalone, phoxim, piriniphos-ethyl, pirmiphos-methyl,profenofos, prothiofos, sulfprofos, triazophos, richlorphon; carbamates,e.g., aldicarb, bendiocarb, carbaryl, carbofuran, carbosulfan,cloethocarb, 2-(1-methylpropyl)phenylmethylcarbamate, butocarboxirme,butoxycarboxime, fenoxycarb, isoprocarb, methomyl, methiocarb, oxamyl,pirimicarb, promecarb, propoxur and thiodicarb; biological insecticides,e.g., products originating from Bacillus thuringiensis; syntheticpyrethroids, e.g., allethrin, alphamethrin, bioresmethrin, bifenthrin,cycloprothiin, cyfluthn, cyhalothrin, cypermeliin, decamethrin,deltamethrin, fenpropatlrn, fenfluthrin, fenvalerate, flucytlirinate,flumethrin, fluvalinate, halothrin, permethrn, resmethrin andtralomethrin,alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropancarboxylate;organosilicon compounds such asdimethylphenylsilylmethyl-3-phenoxybenzylethers e.g.,dimethyl(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzylether; ordimethylphenylsilylmethyl-2-phenoxy-6-pyridylmethylethers e.g.dimethyl(9-ethoxyphenyl)silylmethyl-2-phenoxy-6-pyridylmethylether or[(phenyl)-3-(3-phenoxyphenyl)propyl](dimethyl)silanes e.g.(4-ethoxyphenyl)[3-(4fluoro-3-phenoxyphenyl]propylldimethylsilane,silafluofen; nitroimines and nitromethylenes e.g.1-(6-chloro-3-pyridinyhuethyl)-4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid); benzoylureas e.g. lufenuron, hexaflumuron, flufenoxuron.

Particularly interesting active ingredients for combination with thepresent compositions comprising the active ingredients (I) and (II), inquantities producing a mutual synergistic effect, are: dichlofluanid,tolylfluanid, benzyldimethyldodecyl ammonium chloride, didecyldimethylammonium chloride, 3-bromo-2,3-diiodo-2-propenylalcohol,3-iodo-2-propinyl-n-butylcarbamate, o-phenylphenol, m-phenylphenol,p-phenylphenol, 3-methyl-4-chorophenol,thiocyanatomethyl-thiobenzothiazole, N-methyl-isothiazolin-3-one,5-chloro-N-methylisotiiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one,benzylalkohol-mono(poly)hemiformal, N-methylolchloracetamide, phoxim,cyfluthrin, pennethrin, cypermethrin, deltamethrin, imidacloprid,silafluofen, lufenuron, bifenthrin, fenoxycarb, hexaflumuron,flufenoxuron.

Susceptible material (in particular wood) destroying insects are, forexample:

Beetles: Anobium punctatum Apate monachus Bostrychus capucinusChlorophores pilosus Dendrobium pertinex Dinoderus minutus Ernobiusmollis Heterobostrychus brunneus Hylotrupes bajulus Lyctus africanusLyctus brunneus Lyctus linearis Lyctus planicollis Lyctus pubescensMinthea rugicollis Priobium carpini Ptilinus pecticornis Sinoxylon spp.Trogoxylon aequale Tryptodendron spp. Xestobium rufovillosum Xyleborusspp. Hymenoptera: Sirex juvencus Urocerus augur Urocerus gigas Urocerusgigas taignus. Termites: Coptotermes formosanus Cryptotermes brevisHeterotermes indicola Kalotermes flavicollis Mastotermes darwiniensisReticulitermes flavipes Reticulitermes lucifugus Reticulitermessantonensis Zootermopsis nevadensis.

The synergistic mixtures or compositions to be used directly may also beobtained from separate compositions containing the active ingredients orfrom the technical active ingredients themselves, by mixing and/ordiluting with aqueous or organic media and/or optionally further addingadjuvants such as those described hereinabove. Said separatecompositions generally are such as described hereinbefore forcompositions containing both active ingredients. Of particular interestto some users may be preparation of custom-made formulations from bothactive ingredients in unmodified, technical form, thus allowing maximalflexibility in the application of the present synergistic mixtures ofthe active ingredients (I) and (II).

The present invention also concerns a method of combating fungicomprising treating plants or the loci thereof, or treating plantproducts such as wood; or pulpwood for paper manufacture, or treatingbiodegradable materials simultaneously, separately or sequentially withan effective amount of a synergistic, fungicidal composition asdescribed hereinabove.

The present invention also concerns a method of preserving wood, woodproducts and biodegradable materials from deterioration by fungi. Thismethod comprises the application to or incorporation in said wood orwood products or in or to said biodegradable materials, of a synergisticmixture or composition as defined hereinabove.

The active ingredients (I) and (II) can be applied to plants or to theloci thereof or to plant products, e.g. wood, or to biodegradablematerials such as textiles, simultaneously, or can also be appliedconsecutively within a time period selected so that both activeingredients are allowed to act synergistically as antifungals, e.g.within 24 hours. In such applications, the active ingredients are usedoptionally together with adjuvants conventionally employed in the art offormulation such as carriers, surfactants or other useful additives.Therefore, the present invention also concerns products comprising acompound of formula (I), in particular3-benzo[b]thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine 4-oxide, or a saltthereof, and a compound of formula (II), in particularN-cyclohexylbenzo-thiophene-2-carboxamide-S,S-dioxide (II), or a saltthereof, as a combination for simultaneous, separate or sequential usein fungicidal applications. Such products may consists of a packagecomprising containers with both active ingredients, preferably informulated form. Such formulated forms in general have the samecomposition as described for the formulations containing both activeingredients.

The following examples are intended to illustrate the scope of thepresent invention in all its aspects. Unless otherwise stated all partstherein are by weight.

A. BIOLOGICAL EXAMPLES Example 1

The synergistic activity of the mixtures or compositions of (I) and (II)according to the present invention can be demonstrated by comparisonwith the activity of the active ingredients (I) and (II) alone. Theefficacy of the active ingredients against mycelial growth andsporulation of Aureobasidium pullulans, Aspergillus niger, Scierophomaentoxylina, Trichodenna viride, was determined in the poison plateassay. The required concentrations of the fungicide(s) were obtained bydiluting the active ingredients (I), (II) or the combination of (I) and(II) in dimethyl sulfoxide (DMSO) at 800 times the final testconcentration. The stock solutions in DMSO were pipetted intoPetri-dishes. Malt extract agar (3%) was added aseptically and uniformdistribution was obtained by shaking. Each plate was spot inoculatedwith a spore or mycelial suspension. After incubation at 22° C. and 70%relative humidity for a period long enough to allow complete growth ofcontrols, diameters of colonies were measured. Relative activities werecalculated by taking the absence of fungal growth (diameter 0 mm) as100%. From the activity of the active ingredients alone, the expectedactivities E were calculated by using the so-called formula of Colby:(Colby, S. R. Weeds 1967, 15: 20-22),$E = {X + Y - \frac{X \cdot Y}{100}}$

wherein X and Y express the relative activities obtained for each of theactive ingredients. A synergistic effect can be acknowledged if thefound activity exceeds calculated activity.

The results are listed in the tables 1 to 4 below and clearlydemonstrate that the measured activity generally exceeds the calculatedactivity. Equal efficacy was observed whenever complete inhibition offungal growth occurred by one of the active ingredients (I) or (II)alone. The compound of formula (I) used in the experiment was3-benzo[b]-thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine 4-oxide, i.e.compound (1). The compound of formula (II) used in the experiment wasN-cyclohexyl-benzothiophene-2-carboxamide-S,S-dioxide, i.e. compound(2).

TABLE 1 Activity of compound (1) and compound (2) and their mixturesagainst Aureobasidium pullulans Experiment 1 Experiment 2 Conc. mg/lIncubation period: 5 days Incubation period: 7 days Co. No. Co. No.growth activity % growth activity % (1) (2) mm measured calculated mmmeasured calculated 0.62 0 33 13 — — — — 1.25 0 26 32 — 44 8 — 2.50 0 1561 — 38 21 — 5.00 0 5 87 — — — — 0.62 2.5 29 24 20 — — — 1.25 2.5 22 4237 42 13 10 2.5 2.5 13 66 64 35 27 22 5 2.5 6 84 88 — — — 0.62 5 27 2927 — — — 1.25 5 19 50 42 38 21 14 2.5 5 9 76 67 32 33 26 5 5 5 87 87 — —— 0.62 10 22 42 59 — — — 1.25 10 14 63 57 32 33 16 2.5 10 6 84 75 26 4627 5 10 5 87 92 — — — 0.62 20 16 58 59 — — — 1.25 20 10 74 68 21 56 292.5 20 5 87 81 12 75 39 5 20 5 87 94 — — — 0 2.5 35 8 — 47 2 — 0 5 32 16— 45 6 — 0 10 24 37 — 44 8 — 0 20 18 53 — 37 23 — controls DMSO 38 48

TABLE 2 Activity of compound (1) and compound (2) and their mixturesagainst Aspergillus niger. Experiment 1 Experiment 2 Conc. mg/lIncubation period: 5 days Incubation period: 7 days Co. No. Co. No.growth activity % growth activity % (1) (2) mm measured calculated mmmeasured calculated 0.62 0 42 5 — — — — 1.25 0 38 14 — 38 16 — 2.50 0 2739 — 25 44 — 5.00 0 0 100 — — — — 0.62 2.5 40 9 5 — — — 1.25 2.5 35 2014 37 18 17 2.5 2.5 17 61 39 23 49 46 5 2.5 0 100 100 — — — 0.62 5 39 119 — — — 1.25 5 32 27 18 36 20 17 2.5 5 15 66 41 22 51 46 5 5 0 100 100 —— — 0.62 10 33 25 72 — — — 1.25 10 30 32 33 30 33 23 2.5 10 8 82 53 7 8449 5 10 0 100 100 — — — 0.62 20 17 61 72 — — — 1.25 20 2 95 74 18 60 462.5 20 0 100 82 0 100 64 5 20 0 100 100 — — — 0 2.5 44 0 — 44 2 — 0 5 425 — 44 2 — 0 10 34 23 — 41 9 — 0 20 13 70 — 29 36 — controls DMSO 44 45

TABLE 3 Activity of compound (1) and compound (2) and their mixturesagainst Sclerophoma entoxylina. Experiment 1 Experiment 2 Conc. mg/lIncubation period: 5 days Incubation period: 7 days Co. No. Co. No.growth activity % growth activity % (1) (2) mm measured calculated mmmeasured calculated 0.62 0 42 2 — — — — 1.25 0 37 14 — 47 4 — 2.50 0 2737 — 40 18 — 5.00 0 7 84 — — — — 0.62 2.5 37 14 9 — — — 1.25 2.5 34 2120 45 8 6 2.5 2.5 21 51 42 33 33 20 5 2.5 6 86 85 — — — 0.62 5 37 14 18— — — 1.25 5 35 19 28 45 8 8 2.5 5 22 49 47 32 35 22 5 5 5 88 88 — — —0.62 10 30 30 41 — — — 1.25 10 27 37 30 38 22 20 2.5 10 19 56 49 22 5532 5 10 4 91 87 — — — 0.62 20 22 49 41 — — — 1.25 20 18 58 48 27 45 312.5 20 9 79 62 15 69 42 5 20 5 88 90 — — — 0 2.5 40 7 — 48 2 — 0 5 36 16— 47 4 — 0 10 35 19 — 41 16 — 0 20 26 40 — 35 29 — controls DMSO 43 49

TABLE 4 Activity of compound (1) and compound (2) and their mixturesagainst Trichoderma viride. Experiment 1 Experiment 2 Conc. mg/lIncubation period: 5 days Incubation period: 7 days Co. No. Co. No.growth activity % growth activity % (1) (2) mm measured calculated mmmeasured calculated 0.62 0 49 0 — — — — 1.25 0 49 0 — 43 12 — 2.50 0 482 — 35 29 — 5.00 0 35 29 — — — — 0.62 2.5 49 0 0 — — — 1.25 2.5 49 0 040 18 12 2.5 2.5 42 14 2 34 31 29 5 2.5 36 27 29 — — — 0.62 5 49 0 0 — —— 1.25 5 49 0 0 39 20 12 2.5 5 43 12 2 33 33 29 5 5 33 33 27 — — — 0.6210 48 2 14 — — — 1.25 10 45 8 0 36 27 19 2.5 10 40 18 2 27 45 34 5 10 3039 29 — — — 0.62 20 39 20 14 — — — 1.25 20 36 27 14 31 37 34 2.5 20 2941 16 12 76 46 5 20 22 55 39 — — — 0 2.5 49 0 — 49 0 — 0 5 49 0 — 49 0 —0 10 49 0 — 45 8 — 0 20 42 14 — 37 24 — controls DMSO 49 49

Example 2

The synergistic activity of the mixtures or compositions comprising acompound of formula (O) and a compound of formula (II) according to thepresent invention can be demonstrated by comparison with the activity ofthe active ingredients (I) and (II) alone in preventing destruction ofwood by fimgi versus the efficacy of either active ingredient alone wastested in a wood stick test with Aureobasidium pullulans, Aspergillusniger, Penicillium purpurogenum and Scierophoma entoxylina as testfungi. Oven-dried wood sticks (50×12×2 mm) of Scots Pine (Pinussylvestris) were dipped during 3 hours in a methanol solution comprisinga compound of formula (I), a compound of formula (II), or a combinationof a compound of formula (I) and a compound of formula (II), and allowedto dry overnight in a sterile laminar air flow. In each Petri dish onestick was placed on culture medium, PDA PS (Potato Dextrose Agarcontaining 60 mg penicillin and 200 mg streptomycin), previously seededwith inoculum. Two drops of fungal or spore suspension were pipetted onthe upper surface of the stick The Petri dishes were incubated at 22° C.and 70% relative humidity. The test was evaluated after sufficientgrowth of the fungus on the control sticks. The following score systemwas used:

0: sticks free of fungal growth

1: traces of growth on the stick

2: slight growth (5 to 25% of the surface covered)

3 : moderate growth (25 to 50% of the surface covered)

4: vigorous to maximum growth (more tha 50% covered)

To calculate synergism results were converted to the next artificialactivities:

0: 100% activity

1: 95% activity

2: 75% activity

3: 50% activity

4: 0% activity

Yhe expected activities E were calculated by using the so-called formulaof Colby: (Colby, S. R. Weeds 1967, 15: 20-22),$E = {X + Y - \frac{X \cdot Y}{100}}$

wherein X and Y express the relative activities obtained for each of theactive ingredients. A synergistic effect can be acknowledged if thefound activity exceeds calculated activity.

The compound of formula (I) used in the experiment was3-benzo[b]-thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine 4-oxide, i.e.compound (1). The compound of formula (II) used in the experiment wasN-cyclohexyl-benzothiophene-2-carboxamide-S,S-dioxide, i.e. compound(2).

TABLE 5 Synergistic effects between compound (1) and compound (2) onAureobasidium in a stick test. measured calculated compound (1) compound(2) stick test % overgrown (relative) (expected) in ppm in ppm scores ofthe sticks activity % activity % 200 0 4 100 0 — 400 0 3 50 50 — 0 200 4100 0 — 0 400 2 25 75 — 0 800 1 5 95 — 200 200 3 50 50  0 200 400 1 5 9575 200 800 1 5 95 95 400 400 0 0 100 88 400 800 0 0 100 98 control 4 1000 — DMSO

TABLE 6 Synergistic effects between compound (1) and compound (2) onAspergillus in a stick test. measured calculated compound (1) compound(2) stick test % overgrown (relative) (expected) in ppm in ppm scores ofthe sticks activity % activity % 200 0 4 100 0 — 400 0 3 50 50 — 0 200 4100 0 — 0 400 4 100 0 — 0 800 4 100 0 — 200 200 4 100 0 0 200 400 3 5050 0 200 800 3 50 50 0 400 400 3 50 50 50 400 800 3 50 50 50 control 4100 0 — DMSO

TABLE 7 Synergistic effects between compound (1) and compound (2) onPenicillium in a stick test. measured calculated compound (1) compound(2) stick test % overgrown (relative) (expected) in ppm in ppm scores ofthe sticks activity % activity % 200 0 4 100 0 — 400 0 2 25 75 — 0 200 4100 0 — 0 400 3 50 50 — 0 800 2 25 75 — 200 200 4 100 0  0 200 400 2 2575 50 200 800 1 5 95 75 400 400 2 25 75 88 400 800 1 5 95 94 control 4100 0 DMSO

TABLE 8 Synergistic effects between compound (1) and compound (2) onSclerophoma in a stick test. measured calculated compound (1) compound(2) stick test % overgrown (relative) (expected) in ppm in ppm scores ofthe sticks activity % activity % 200 0 4 100 0 — 400 0 3 50 50 — 0 200 4100 0 — 0 400 4 100 0 — 0 800 2 25 75 — 200 200 4 100 0 0 200 400 4 1000 0 200 800 0 0 100 75 400 400 1 5 95 50 400 800 0 0 100 88 Control 4100 0 DMSO

What is claimed is:
 1. A composition comprising the compound3-(benzo[b]thien-2-yl)-5,6-dihydro-1,4,2-oxathiazine,4-oxide, or a saltform thereof, and the compoundN-cyclohexylbenzothiophene-2-carboxamide-S,S,-dioxide, or a salt formthereof in quantities producing a synergistic fungicidal effect, and acarrier.
 2. A composition according to claim 1 wherein the ratio byweight between the compound of formula (I) and the compound of formula(II) is from 50:1to 1:50.
 3. A composition according to claim 1 whereinthe ratio by weight between the compound of formula (I) and the compoundof formula (II) is from 10:1 to 1:10.
 4. A composition according toclaim 1 wherein the ratio by weight between the compound of formula (I)and the compound of formula (II) is from 1:4 to 1:2.
 5. A compositionaccording to claim 1 further comprising a copper compound.
 6. Acomposition according to claim 1 further comprising a fungicidallyactive triazole.
 7. A method for protecting wood, wood products,biodegradable materials or coatings comprising applying a composition ofclaim 1 to said wood, wood products, biodegradable materials orcoatings.
 8. A product containing the compound3-(benzo[b]thien-)-yl-5,6,-dihydro-1,4,2-oxathiazine, 4-oxide, or a saltthereof, and the compound N-cyclohexylbenzothiophene or a salt thereof,as a combination for simultaneous, separate or sequential use infungicidal applications.